• Journal of the Korean Applied Science and Technology
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• v.7 no.1
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• pp.93-105
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• 1990

Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.

• Journal of the Korean institute of surface engineering
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• v.34 no.5
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• pp.414-420
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• 2001

A 30-kV plasma immersion ion implantation setup (P $I^3$) has been equipped with a self-developed 6'-magnetron to perform hard coatings with enhanced adhesion by P $I^3$D(P $I^3$ assisted deposition) process. Using ICP source with immersed Ti antenna and reactive magnetron sputtering of Ti target in $N_2$/Ar ambient gas mixture, the TiN films were prepared on Si substrates at different pulse bias and ion-to-atom arrival ratio ( $J_{i}$ $J_{Me}$ ). Prior to TiN film formation the nitrogen implantation was performed followed by deposition of Ti buffer layer under A $r^{+}$ irradiation. Films grown at $J_{i}$ $J_{Me}$ =0.003 and $V_{pulse}$=-20kV showed columnar grain morphology and (200) preferred orientation while those prepared at $J_{i}$ $J_{Me}$ =0.08 and $V_{pulse}$=-5 kV had dense and eqiaxed structure with (111) and (220) main peaks. X-ray diffraction patterns revealed some amount of $Ti_{x}$ $N_{y}$ in the films. The maximum microhardness of $H_{v}$ =35 GN/ $M^2$ was at the pulse bias of -5 kV. The P $I^3$D technique was applied to enhance wear properties of commercial tools of HSS (SKH51) and WC-Co alloy (P30). The specimens were 25-kV PII nitrogen implanted to the dose 4.10$^{17}$ c $m^{-2}$ and then coated with 4-$\mu\textrm{m}$ TiN film on $Ti_{x}$ $N_{y}$ buffer layer. Wear resistance was compared by measuring weight loss under sliding test (6-mm $Al_2$ $O_3$ counter ball, 500-gf applied load). After 30000 cycles at 500 rpm the untreated P30 specimen lost 3.10$^{-4}$ g, and HSS specimens lost 9.10$^{-4}$ g after 40000 cycles while quite zero losses were demonstrated by TiN coated specimens.s.

• Journal of Environmental Science International
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• v.2 no.1
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• pp.61-72
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• 1993

Result of this study indicate that two criteria must be met in order to have effective macrocycle-mediated transport in these emulsionsystem. First, one must effective extraction of the post transition metals, $Cd^{2+}$. $Pb^{2+}$ and $Hg^{2+}$ , into toluene membrane. The effectiveness of this extraction is greatest if log K values for the metal-macrocycle interaction is large. Second, the ratio of the log K values for the metal ion-receiving phase to the metal ion-macrocycle interaction must be large enough to ensure quantitative stripping of the metal ion at the toluene phase interface. Control of the first step can be obtained by appropriate selection of macrocycle donor atom, substituents, and cavity radius. The second step can be controlled by selecting the proper complexing agent for inclusion in the receiving phase. The order of the transport, when using the several $A^-$ species such as $SCN^-$, $1^-$, $Br^-$ and $Cl^-$ is the order of the changing degree of solvation for $A^-$ and the transport of the metals is also affected by the control of concentration for receiving species because of solubility-differences. In this study, we can seperate each single metal ion from the mixture of $Cd^{2+}$, $Pb^{2+}$, and $Hg^{2+}$ ions by using the toluene membranes controlled by optimized conditions. Transport of the single metal is also very good, and alkaline and alkaline earth metals as interferences ions did not affect the seperation of the metals in this macrocycle-liquid membrances but transition metal ions were partially affected as interferences for the post transition metal ions.

• Applied Chemistry for Engineering
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• v.32 no.3
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• pp.290-298
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• 2021

A purification process was performed for the application of natural graphite as an anode material. The influence of the structural change and impurity content of graphite according to the process on the anode electrochemical characteristics was investigated. Natural graphite was chemically/physically purified by acid-treatment which used different amounts of solution of ammonium fluoride/sulfuric acid in the same ratio and thermal treatment used different temperatures (800~2500 ℃). Acid-treatment had limitation to remove impurities, and identified that all impurity contents was removed except some traces of atom such as Si by after progressed thermal-treatment until 2500 ℃. The anode materials characteristic of graphite treated by purification process was improved, and changes in the structure and impurity contents affected dominantly the capacity, rate property and initial Coulombic efficiency. Consequently, the complex purification process improved the graphite structure and also the performance of lithium ion battery by controlling the excessive formation of solid electrolyte interphase and expanding Li⁺ insertion space originated from the effective removal of impurities.

• Bulletin of the Korean Chemical Society
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• v.14 no.5
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• pp.561-567
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• 1993

The twelve macrocycle (L) complexes of cadmium(II) nitrate have been synthesized: $CdL(NO_3)_2$. All the complexes have been indentified by elemental analysis, electric conductivity measurements, IR and NMR spectroscopic techniques. The molar electric conductivities of the complexes in water and acetonitrile solvent were in the range of 236.8-296.1 $cm^2{\cdot}mol^{-1}{\cdot}ohm^{-1}$ at 25$^{\circ}$C. The characteristic peaks of macrocycles affected from Cd(II) were shifted to lower frequencies as compared with uncomplexed macrocycles. A complex with 1,4,8,11-tetrakis(methylacetato)-1,4,8,11-tetraaza cyclodecane (L4) exhibited two characteristic bands such as strong stretching (1646 $cm^{-1})$, and weaker symmetric stretching band (1384 $cm^{-1})$. NMR studies indicated that all nitrogen donor atoms of macrocycles have greater affinity to cadmium(II) metal ion than do the oxygen atoms. The $^{13}$C-resonance lines of methylene groups neighboring the donor atom such as N and S were shifted to a direction of high magnetic field and the order of chemical shifts were $L_1 < L_2 < L_3 < L_6 < L_4$. Also the chemical shifts values were larger than those of methylene groups bridgeheaded in side-armed groups. This result seems due to not only the strong interaction of Cd(Ⅱ) with nitrogen donors according to the HSAB theory, but weak interaction of Cd(Ⅱ) and COO- ions or sulfur which is enhanced by the flexible methylene spacing group in side-armed groups. Thus, each additional gem-methyl pairs of L_3, L_4\;and\; L_6$ macrocycles relative to $L_1, L_2,\;and\;L_5$ leads to an large enhancement in Cd(II) affinity. ^{13}C$-NMR spectrum of the complex with $L_{12}$ (1,5,9,13-tetracyclothiacyclohexadecane-3,11-diol) reveals the presence of two sets of three resonance lines, and intensities of the each resonance line have the ratio of 1 : 2 : 2. This molecular conformation is predicted as structure of tetragonal complex to be formed by coordinating two sulfur atoms and the other two sulfur atoms which is affected by OH-groups.

• Bulletin of the Korean Chemical Society
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• v.11 no.4
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• pp.276-281
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• 1990

The equivalent conductance of univalent cation (potassium, silver, thallium and ammonium) perchlorates in methanol containing 18-membered crown ethers, 18-crown-6 (18C6) and 1,10-dithia-18-crown-6 (DT18C6) were measured at different temperatures. The equivalent conductances of ammonium perchlorate were increased by increasing content of DT18C6 exceptionally, due to more favorable solvations than complexations. From the equivalent conductance changes, the formation constants for 1:1 compmlexes have been determined, and the values of enthalpy and entropy changes have been calculated. The complexations of 18C6 and DT18C6 with the univalent cations under investigation are all exothermic and the ${\Delta}$S values are all negative and no considerable differences around 50 J/ (k mol). The selectivity order of 18C6 is $K^+ > Tl^+ > Ag^+ > NH_4^+$, while that of DT18C6 is $Ag^+ > Tl^+ > NH_4^+ > K^+$. By sulfur substitutions in 18C6 result in significant decrease in stability, but the stability of $Ag^+$-DT18C6 complex are $10^4$ times larger than those of $K^+$. This increase of stabilities for $Ag^+$-DT18C6 complex are primary due to the result of favorable exothermic heat of reaction between the polarizable soft cation and soft sulfur centers. In NMR experiment, the stepwise additions of cation perchlorates into crown ether solutions induced two major spectral changes. First, the resonance all shift down field and the cation induced shifts were linear up to 1:1 cation/crown ratio, above which no further changes were observed. On the basis of these results, it could be concluded that 1:1 complex is formed. Second, the magnitudes of cation induced shifts were different each other in same ligand. By addition of silver ion to the solution of DT18C6, the largest shift of proton peak near the sulfur atom was observed. These effects are also arisen from the results of covalent bonding between "soft-soft" interactions.

• Journal of the Korean Ceramic Society
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• v.30 no.4
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• pp.289-298
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• 1993

Properties in terms of the variation of the glass compositions, which were density (p), molar volume(Vm), atom/ion packing density (Dp), refractive index (nD), transformation temperature (Tg), dilatometric softening point (Td), thermal expansion coefficient (α), Young's modulus (E), and knoop hardness (KHN) were investigated in CaO-SiO2 glasses and CaO-P2O5-SiO2 glasses containing less than 10mole% of P2O5. Those properties were measured by density measurement kit, Abbe refractometer, dilatometer, ultrasonic pulse echo equipment, and micro hardness tester. When CaO content was increased in CaO-SiO2 glasses, p, Dp, nD, Tg, Td, α, E and KHN were increased, while Vm was decreased. When P2O5 was added to the CaO-SiO2 glasses with constant CaO/SiO2 ratio as 1.07, p, Dp, nD, Tg, Td, α, E and KHN were decreased, while Vm was increased. When the amount of P2O5 in glasses was kept constant, the changes of the properties with variation of CaO content in the CaO-P2O5-SiO2 glasses were very similar to those of CaO-SiO2 glasses. These phenomena could be explained by the structural role of P2O5 in the CaO-P2O5-SiO2 glasses, which was polymerization of siicate structures and resulted in [PO4] monomer structure in glasses. Due to this structural characteristics, the bond strength and packing density were changed with compositions. Proportional relationships between 1) np and Dp, 2) Tg, Td, α and CaO content, 3) E and Vm-1, and 4) KHN and P2O5 content were evaluated in this investigation.

• Applied Biological Chemistry
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• v.10
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• pp.1-13
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• 1968

Phytin is a salt(mainly calcium and magnesium) of phytic acid and its purity and molecular formula can be determined by assaying the contents of phosporus, calcium and magnesium in phytin. In order to devise a new method for the quantitative analysis of the three elements in phytin, the chelatometric method was developed as follows: 1) As the pretreatment for phytin analysis, it was ashfied st $550{\sim}600^{\circ}C$ in the presence of concentrated nitric acid. This dry process is more accurate than the wet process. 2) Phosphorus, calcium and megnesium were analyzed by the conventional and the new method described here, for the phytin sample decomposed by the dry process. The ashfied phytin solution in hydrochloric acid was partitioned into cation and anion fractions by means of a ration exchange resin. A portion of the ration fraction was adjusted to pH 7.0, followed by readjustment to pH 10 and titrated with standard EDTA solution using the BT [Eriochrome black T] indicator to obtain the combined value of calcium and magnesium. Another portion of the ration fraction was made to pH 7.0, and a small volume of standard EDTA solution was added to it. pH was adjusted to $12{\sim}13$ with 8 N KOH and it was titrate by a standard EDTA solution in the presence of N-N[2-Hydroxy-1-(2-hydroxy-4-sulfo-1-naphytate)-3-naphthoic acid] diluted powder indicator in order to obtain the calcium content. Magnesium content was calculated from the difference between the two values. From the anion fraction the magnesium ammonium phosphate precipitate was obtained. The precipitate was dissolved in hydrochloric acid, and a standard EDTA solution was added to it. The solution was adjusted to pH 7.0 and then readjusted to pH 10.0 by a buffer solution and titrated with a standard magnesium sulfate solution in the presence of BT indicator to obtain the phosphorus content. The analytical data for phosphorus, calcium and magnesium were 98.9%, 97.1% and 99.1% respectively, in reference to the theoretical values for the formula $C_6H_6O_{24}P_6Mg_4CaNa_2{\cdot}5H_2O$. Statical analysis indicated a good coincidence of the theoretical and experimental values. On the other hand, the observed values for the three elements by the conventional method were 92.4%, 86.8% and 93.8%, respectively, revealing a remarkable difference from the theoretical. 3) When sodium phytate was admixed with starch and subjected to the analysis of phosphorus, calcium and magnesium by the chelatometric method, their recovery was almost 100% 4) In order to confirm the accuracy of this method, phytic acid was reacted with calcium chloride and magnesium chloride in the molar ratio of phytic: calcium chloride: magnesium chloride=1 : 5 : 20 to obtain sodium phytate containing one calcium atom and four magnesium atoms per molecule of sodium phytate. The analytical data for phosporus, calcium and magnesium were coincident with those as determine d by the aforementioned method. The new method employing the dry process, ion exchange resin and chelatometric assay of phosphorus, calcium and magnesium is considered accurate and rapid for the determination of phytin.